title: Synthesis and characterization of Pd complexes of a carbazolyl/bis(imine) NNN pincer ligand.
abstract: A serendipitously discovered construction of a carbazole nucleus by lithiation of N-methylated bis(4-methyl-2,6-dibromophenyl)amine is described. It was used to synthesize an NNN pincer-type ligand that combines a central carbazole site (N-methylated in the precursor ligand) with two flanking aldimine donors bearing mesityl substituents. The installation of this ligand on Pd was accomplished via an N-Me cleaving reaction with (COD)PdCl(2) producing MeCl and (NNN)PdCl (where NNN is an anionic carbazolyl/bis(imine) pincer ligand). Several (NNN)PdX complexes were characterized spectroscopically. (NNN)PdOTf ((-)OTf = triflate or (-)O(3)SCF(3)) readily reacted with stoichiometric amounts of water in benzene or dichloromethane to give a cationic water adduct [(NNN)Pd(OH(2))]OTf. An X-ray diffraction study on a single crystal of (NNN)PdCl revealed an almost perfectly square planar environment about Pd and an almost perfectly planar carbazole/bis(imine) conjugated system. Cyclic voltammetry of (NNN)PdCl showed quasi-reversible oxidation at E(1/2) = 0.72 V vs Fc/Fc(+) which is most likely ligand-based.
authors.affiliation: Department of Chemistry, Texas A&M University, 3255 TAMU, College Station, Texas 77842, USA.
authors.forename: Aaron M
authors.initials: AM
authors.lastname: Hollas
authors.forename: Weixing
authors.initials: W
authors.lastname: Gu
authors.forename: Nattamai
authors.initials: N
authors.lastname: Bhuvanesh
authors.forename: Oleg V
authors.initials: OV
authors.lastname: Ozerov